Production of photographic and cinematographic color images



Patented Feb. 23, 1943 PRODUCTION OF PHOTOGRAPHIC AND CINEMATOGRAPHIC COLOR IMAGES Wilhelm Schneider and Alfred Friihlich, Dessan, Germany, assilnors to General Aniline & Film Corporation, New York, N.

Delaware No Drawing.

Y., a corporation of Application September 5, 1940, Se-

m1 No. 355,458. In Germany July 5, 1939 6 Claims.

This invention relates to the production of photographic and cinematographic color images. For the production of photographic and cine matographic color images there are generally employed silver halide emulsions to which before casting or during any stage of the manufacturing process there are added dyestuif components fast to diffusion which may be converted into a color image after exposure of the photographic emulsion by a suitable process, directly or indirectly, by means of the latent image or silver image. Suitable color formers have been described in great numbers. In the U. S. Patent 2,179,238 there are mentioned color formers with substantive groups which impart a certain aflinity of the color formers to the layer-forming colloid, for instance diphenyl or stilbene. Furthermore there are described in U. S. Patent 2,178,612 color formers with radicals of high polymeric acids, in U. S. Patent 2,186,849 color formers with long carbon chains, in U. S. Patent 2,179,244 color formers with polypeptide radicals, in U. S. Patent 2,186,732 color formers with carbohydrate radicals, in U. S. Patent 2,186,733 color formers with resin acid radicals, in U. S. Patent 2,186,851 color formers with bile acid radicals, in U. S. Patent 2,280,722 color formers with substituents having several members, in which besides the initialand end members the same carbon-arrangements occur several times being connected by hetero atoms, such as for instance polyethylene imineor polyethylene oxide radicals, finally in U. S. Patent 2,307,399 and U. S. patent appliactions, Ser. No. 333,813, filed May 7, 1940, and Ser. No. 335,144, filed May 14, 1940, color formers with radicals of other polymerisates containing nitrogenor hydroxyl groups. In these color formers there is accomplished the union of the color former-molecule with the molecule-radicals effecting fastness to diffusion from a practical view point mostly in the form of an acid amide linkage, and it is immaterial on which of the reactants the aminoor acid group is found.

Color formers of this kind are for instance the following compounds which are selected at will from the great number of known dyestuffs described in former patent applications:

a-hydroxy-naphthoic acid benzidide, the reaction products of a-hydroxy-naphthoic acid with 4,4'-diamino stilbene 1,2,3,4-xylenol-car- 'boxylic acid with dodecylamine, fi-methoxy-salicylic acid with octadecylamine, salicylic acid with cerylamine, a-hydroxy-naphthoic acid with abietylamine, the condensation product from stearic acid and u-hydroiw-naphthoyl-4-amino- 3-sulfo acid anilide, the reaction products of 2- amino-l-naphthol with abietic acid, 1-amino-8- naphthol with cholanic acid, 1-amino-8-naphthol-6,7-disulfo acid with lauric acid, 1-amino-8- naphthol-7-sulfo acid wily abietic acid, a-hydroxy-naphthoic acid witffcholesterylamine, ahydroxy-anthracene-carboxylic acid with dodecylamine, salicylic acid with dodecylamine, ahydroxy-fi-methoxy-2-naphthoic acid with octadecylamine, a-hydroxy-naphthoic acid with pamino-methyl-dodecylaniline-2-sulfo acid, 2 mol a-hydroxynaphthoic acid and stearylamino-pphenyienediamine. These color formers are most suitable for the manufacture of multicolor photographic material for multicolor photography, especially in silver halide emulsion layers, which according to U. S. Patents 2,148,979 and 2,148,980 are sensitized with sensitizers the sensitizing effect of which is not influenced by the color formers. These color formers, however, show a considerable disadvantage which becomes evident especially when the material manufactured with these color formers is stored under conditions prevailing in warm countries. To store photographic materials containing these color formers in warm countries, changes the sensitization of the photographic material. Consequently insufiicient and absolutely incorrect color reproduction is obtained therefrom. The effect of the color formers, namely to injure the sensitivity of the emulsions can evidently be traced to the fact, that the color formers have a great tendency to be adsorbed on the silver halide grain. They therefore push aside the sensitizer from the place of its effectiveness. formers does not become manifest in the first instance, but it is evident when the photographic materials manufactured with these color formers are stored for a long period. This detrimental property of a color former can be found out at once, by adding the color components to the unsensitized silver halide emulsion before the sensitizing dyestuffs. In this case the sensitizer being added afterwards cannot tinge the silver halide grain, since this is evidently occupied by the color component. Consequently the sensitizing effect is not at all present or to a very low degree only.

It is an object of this invention to produce photographic color formers fast to diffusion.

Another object is to manufacture color formers not injuring the sensitization of the photographic emulsion.

A further object is to manufacture a photo- This tendency of the color images containing color overcome when such color formers fast to diffusion are employed, which do not influence fundamentally the sensitivity of the silver halide emulsions,

though they are incorporated in the silver halide emulsions before adding the sensitizer thereto. The capability of adsorption of the color former by the silver halide grain and consequently the low keeping quallity of the photographic materials containing these color formers were found to be caused 'by the acid hydrogen of the imino group, if the imino group is in orthoor periposition to the hydroxyl group participating in the formation of the dyestuff. The acid hydrogen of the imino group, for instance, may be present in the following atom groupings: -NHCO-, -CONH, -SO2NH-, -NH-SO2--, NH-CO-NH and -NH-CS-NH.

According to the present invention there are employed dyestufi components fast to diffusion which in orthoor peri-position to the hydroxyl group participating in the formation of the dyestuff do not contain any radicals with free iminohydrcgen. Other suitable color formers are those which are obtained by the action of a primary amine fast to diffusion on an aromatic hydroxy acid capable of coupling, in which the acid group is not located in a position ortho or peri to the hydroxyl group, color formers which are obtained by the action of secondary amines fast to diffusion on compounds containing hydroxy groups and capable of coupling, color formers which are obtained by the action of carboxylic acids or sulfo acids fast to diffusion on secondary amino groups of color components containing hydroxy groups, color formers which are obtained by the action of carboxylic acids or sulfo acids or their derivatives fast to diffusion on primary amino groups being not in orthoor peri-position to the hydroxy group of the dyestuff component, color formers with imino groups which are not in ortho- Or periposition to the hydroxyl group participating in the formation of the dyestuff, and color formers which do not possess any ureaor thiourea-like group in orthoor peri-position to the hydroxyl group participating in the dyestuff formation.

Color formers according to the present inventicn are for instance the reaction products of 1- amino-S-naphthol-B-sulfo acid with palmitic acid, m-hydroxybenzoic acid with oleylamine, oz-

hydroxy-naphthoic acid with methyldodecylgroups, furthermore condensation products from salicyclic acid and phenols and reaction products of hydroxy carboxylic acids with such polyamides as contain preferably secondary amino groups.

When considering the aforementioned rules of 1-amino-5-naphthol-6-sulfo acidspeaking, color formers and molecule radicals effecting fastness to diffusion which wer already proposed in former U. S. Patents: 2,179,238, 2,178,612, 2,186,849, 2,179,244, 2,186,732, 2,186,733, 2,186,851, 2,186,734, 2,186,719, 2,186,852, 2,280,722, 2,292,575 and 2,307,399 and U. S. Patent applications Ser. No. 284,258, filed July 13, 1939, Ser. No. 333,813, filed May 7, 1940 and Ser. No. 335,144, filed May 14, 1940. The color formers may con tain, besides the radicalsv effecting fastness to diffusion, groups effecting increased water-solubility, such as carboxy-, sulfoor hydroxyl groups.

The color formers according to the present invention show contrary to the color components hitherto proposed the surprising effect that they exhibit no affinity whatsoever to the silver halide grain, or in other words they do not prevent tinting of the silver halide grains by the sensitizers.

, The sensitization is therefore influenced in no constitution there may be combined, generally way. This property of the color components which guarantees the good keeping quality of the emulsion containing the same even under trying weather conditions may be clearly seen from the fact that for the same degree of sensitization is effected whether the color component is added to the emulsion before or after the sensitizer. With the aid of these new color components fast to diffusion which avoid the unfavorable constitution of those hitherto used, materials for color photography of increased keeping quality even under unfavorable storage conditions may be manufactured. When manufacturing the photographic material, it is of no importance whether the sensitizer is added to the emulsion before or after the color component. This is of great advantage in cases, where the color component must be added to the emulsion during a certain phase of the manufacturing process, whereas the sensitizer is as usual added at the end of' the process.

The silver halide emulsions containing color formers fast to diffusion may be subjected before casting to a short washing process and may be worked up into photographic layers in a known manner. These layers may be arranged on one or both sides of a support, one on top of the other, and may be sensitized for different spectral regions.

The silver halide emulsions, however, can also be worked up according to U. S. Patent 2,186,730 by arranging on a support, in the form of minute particles, differently sensitized emulsions containing different color formers.

The production of the color images may be accomplished in different ways, for instance according to U. S. Patents Nos. 2,179,228, 2,179,238, 2,186,849, 2,178,612 and U. S. patent application Ser. No. 111,250, filed November 17, 1936. After exposure of the emulsion layers the color images may be produced by a simple color forming development or by reversal development according to U. S. Patents 2,179,234 and 2,229,137.

What we claim is:

1. In a process for the production of a color photographic silver halide emulsion containing a sensitizer and a dyestufi former fast to diffusion, the improvement which comprises adding to a photographic silver halide emulsion a phenolic dyestuff former having linked to a carbon atom of the nucleus thereof a radical rendering the dyestuff former fast to diifusion, said radical being linked to a carbon atom of the phenolic dyestufi' former in a position other than that selected from the class consisting of the orthoand peri-positions to the phenolic hydroxy group by a linkage selected from the class consisting of NHCO, CONH, SO2NH-, NHSO2-, --NHCONH and NHCSNH and then adding to said silver halide emulsion a sensltizer therefor.

2. The process as defined in claim 1 wherein the dyestuff former is the reaction product of a primary amine fast to diflusion and an aromatic hydroxy acid, the acid group of which is in a position other than a position selected from the class consisting of the orthoand pen-positions to the hydroxy group.

3. Theprocess as defined in claim 1 wherein the dyestuff former is the reaction product of a secondary amine fast to difiusion and an aromatic hydroxy acid in which the acid group is in a position other than a position selected from the class consisting of the orthoand peri-positions to the hydroxy group.

4. The process as defined in claim 1 wherein the phenolic dyestuflc former is I-amino-S-naphthol-8-sulfo acid, wherein the radical rendering the dyestufi former fast to diffusion is palmit'yl. and wherein the linkage between said dyestuff former and said radical rendering the dyestufl former fast to diffusion is NHCO.

5. The process as defined in claim 1 wherein the phenolic dyestufi former is metahydroxybenzoic acid, wherein the radical rendering the dyestuif former fast to diffusion is oleyl, and wherein the linkage between said phenolic dyestufi former and said radical rendering the dyestufi former fast to diffusion is CONH-.

6. The process as defined in claim 1 wherein the phenolic dyestufi former is a-hydroxy-naphthoic acid, wherein the radical rendering said phenolic dyestufi former fast to diffusion is methyldodecyl and wherein the linkage between said phenolic dyestuif former and said radical rendering the dyestufl fast to diffusion is CONH-.

WILHELM SCHNEIDER. ALFRED FR6HLICH. 

